Copper Hyper-Stoichiometry: The Key for the Optimization of Thermoelectric Properties in Stannoidite Cu8+xFe3–xSn2S12

5 years ago

Copper Hyper-Stoichiometry: The Key for the Optimization of Thermoelectric Properties in Stannoidite Cu8+xFe3–xSn2S12

Emmanuel Guilmeau, Ramzy Daou, Gérard Le Caër, Pierric Lemoine, Ventrapati Pavan Kumar, Vincent Caignaert, Tristan Barbier, Bernard Raveau, Bernard Malaman

A univalent copper hyper-stoichiometric stannoidite Cu_8+xFe_3–xSn₂S₁₂ with 0 ≤ x ≤ 0.5 has been synthesized using mechanical alloying followed by spark plasma sintering. The X-ray diffraction analysis combined with ⁵⁷Fe and ¹¹⁹Sn Mössbauer investigations has allowed the charge distribution of the cationic species on the various sites to be established and suggests the possibility of a small tin deficiency. The transport properties show a remarkable crossover from a semiconducting to a metal-like behavior as the copper content increases from x = 0 to x = 0.5, whereas correlatively the Seebeck coefficient decreases moderately, with S values ranging from 310 to 100 μV/K. The thermal conductivity decreases as the temperature increases showing low values at high temperature, far below those reported in related stannite materials. The investigation of the thermoelectric properties shows that the ZT figure of merit is dramatically enhanced by the copper hyper-stoichiometry by a factor of 5 going from 0.07 for x = 0 to 0.35 for x = 0.5 at 630 K. This thermoelectric behavior is interpreted on the basis of a model involving the Cu–S framework as the conducting electronic network where the Fe²⁺/Fe³⁺ species play the role of hole reservoir.

Publisher URL: http://dx.doi.org/10.1021/acs.jpcc.7b02068

DOI: 10.1021/acs.jpcc.7b02068